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United States Patent |
5,095,062
|
Winter
,   et al.
|
March 10, 1992
|
Stabilized compositions containing liquid substituted 2H-benzotriazole
mixtures
Abstract
Liquid substituted, 2H-benzotriazole mixtures are prepared by alkylation
with concomitant dealkylation, fragmentation and realkylation of
2-(2-hydroxy-5-alkylphenyl)-2H-benzotriazoles or of
2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazoles with straight or
branched alkenes of 8 to 30 carbon atoms in the presence of an acid
catalyst at 100.degree.-200.degree. C. The liquid mixtures exhibit
outstanding efficacy in protecting organic substrates from light induced
deterioration as well as good resistance to loss by volatilization or
exudation during the processing of stabilized compositions at elevated
temperatures.
Inventors:
|
Winter; Roland A. E. (Armonk, NY);
Detiefsen; Robert E. (Putnam Valley, NY);
Stegmann; Werner (Liestal, CH);
Luisoli; Reto (Holstein, CH);
Leppard; David (Marly, CH)
|
Assignee:
|
Ciba-Geigy Corporation (Ardsley, NY)
|
Appl. No.:
|
578059 |
Filed:
|
September 5, 1990 |
Current U.S. Class: |
524/91; 252/401; 548/260 |
Intern'l Class: |
C08K 005/347.2 |
Field of Search: |
524/91
548/260
252/401
|
References Cited
U.S. Patent Documents
3004896 | Oct., 1961 | Heller et al. | 424/59.
|
3055896 | Sep., 1962 | Boyle et al. | 548/260.
|
3072585 | Jan., 1963 | Milionis et al. | 528/396.
|
3074910 | Jan., 1963 | Dickson | 524/91.
|
3189615 | Jun., 1965 | Heller et al. | 524/91.
|
3230194 | Jan., 1966 | Boyle | 524/91.
|
3253921 | May., 1966 | Sawdey | 430/17.
|
3983132 | Sep., 1976 | Strobel | 524/91.
|
4042394 | Aug., 1977 | Smith, Jr. et al. | 430/17.
|
4096242 | Jun., 1978 | Strobel | 429/59.
|
4127586 | Nov., 1978 | Rody et al. | 524/91.
|
4129521 | Dec., 1978 | Strobel | 524/91.
|
4278590 | Jul., 1981 | Dexter et al. | 524/91.
|
4283327 | Aug., 1981 | Dexter et al. | 524/91.
|
4383863 | May., 1983 | Dexter et al. | 106/125.
|
4447511 | May., 1984 | Dexter et al. | 430/15.
|
4587346 | May., 1986 | Winter et al. | 548/260.
|
4675352 | Jun., 1987 | Winter et al. | 524/91.
|
4973701 | Nov., 1990 | Winter et al. | 548/260.
|
Primary Examiner: Morgan; Kriellion S.
Assistant Examiner: Yoon; Tae H.
Attorney, Agent or Firm: Hall; Luther A. R.
Parent Case Text
This is a divisional of application Ser. No. 179,737, filed on Apr. 11,
1988, now U.S. Pat. No. 4,973,701, issued on Nov. 27, 1990.
Claims
What is claimed is:
1. A stabilized composition which comprises
(a) an organic polymer subject to light-induced deterioration, and
(b) an effective stabilizing amount of a normally liquid or non-crystalline
mixture of benzotriazoles, suitable for stabilizing an organic polymer
against light-induced deterioration, which consists essentially of
compounds of formula I
##STR7##
wherein T.sub.1 is hydrogen, chloro, alkyl of 1 to 4 carbon atoms or
alkoxy of 1 to 4 carbon atoms, and in major proportions compounds
where one of T.sub.2 or T.sub.3 is a random statistical mixture of at least
three isomeric alkyl groups each having 8 to 40 carbon atoms; and
the other of T.sub.2 or T.sub.3 is hydrogen or methyl, and
where one of T.sub.2 or T.sub.3 is a random statistical mixture as defined
above and the other of T.sub.2 or T.sub.3 is alkyl of 2 to 12 carbon
atoms, cycloalkyl of 5 to 8 carbon atoms or aralkyl of 7 to 9 carbon
atoms; and
in minor proportions compounds where both of T.sub.2 and T.sub.3 are a
random statistical mixture as defined above or where the compounds
represent dealkylated or fragmented-alkyl substituted products of the
benzotriazoles of formula I
which mixture is prepared by reacting a 2H-benzotriazole of formula (A) or
(B)
##STR8##
where R.sub.1 is hydrogen, chloro, alkyl of 1 to 4 carbon atoms or alkoxy
of 1 to 4 carbon atoms,
R.sub.2 is alkyl of 2 to 12 carbon atoms, cycloalkyl or 5 to 8 carbon atoms
or aralkyl of 7 to 9 carbon atoms,
G.sub.1 has the same meaning as R.sub.1, and
G.sub.2 and G.sub.3 are independently branched alkyl of 3 to 12 carbon
atoms, cycloaklyl of 5 to 8 carbon atoms or aralkyl of 7 to 9 carbon
atoms, or one of G.sub.2 and G.sub.3 is methyl or ethyl when the other of
G.sub.2 and G.sub.3 is branched alkyl, cycloalkyl or aralkyl as defined
above,
with a straight or branched chain alkene of 8 to 40 carbon atoms or mixture
of said alkenes in the presence of an acidic catalyst at a temperature of
100.degree. to 200.degree. C.
2. A stabilized composition according to claim 1, wherein the organic
polymer is a polyolefin, a styrene polymer, a polyacrylate, a polyamide, a
polyurethane, a halogen containing vinyl polymer, an alkyd resin, a
thermoset acrylic resin or an epoxy resin.
3. A composition according to claim 1 wherein the compounds of formula I,
T.sub.1 is hydrogen or chloro.
4. A composition according to claim 3 wherein T.sub.1 is hydrogen.
5. A composition according to claim 1 where in the compounds of formula I,
T.sub.2 or T.sub.3 in the random statistical mixture of alkyl groups is
alkyl of 8 to 16 carbon atoms.
6. A composition according to claim 5 wherein T.sub.2 or T.sub.3 is alkyl
of 10 to 12 carbon atoms.
7. A composition according to claim 1 where in the compounds of formula I,
T.sub.2 or T.sub.3 is hydrogen, branched alkyl of 4 to 8 carbon atoms or
.alpha.,.alpha.-dimethylbenzyl, but T.sub.2 and T.sub.3 are not both
hydrogen at the same time.
Description
BACKGROUND OF THE INVENTION
The present invention relates to selected liquid 2-aryl-2H-benzotriazoles
which are useful in protecting light-sensitive organic materials from
deterioration and to stabilized compositions containing said
benzotriazoles.
The UV-absorber of the o-hydroxyphenyl-2H-benzotriazole class have long
been known as effective light stabilizers for organic materials and have
enjoyed considerable commercial success.
The description, preparation and uses of these valuable
2-aryl-2H-benzotriazoles are further taught in U.S. Pat. Nos. 3,004,896;
3,055,896; 3,072,585; 3,074,910; 3,189,615 and 3,230,194.
However the hitherto known 2-aryl-2H-benzotriazoles of this group have in
some circumstances exhibited limited compatibility in certain substrates,
and excessive tendency to exude, sublime and/or volatilize during
processing of stabilized compositions into sheets, films, fibers or other
pellicles when processing must be done at elevated temperatures. Likewise
such benzotriazoles may also suffer undue loss by volatilization or
sublimation from fabricated structures, particularly thin films or
coatings, especially when subjected to elevated temperatures during use.
Attempts have been made to increase compatibility and to reduce
volatilization loss by modifying the structure of the benzotriazoles.
In U.S. Pat. No. 3,230,194, a higher alkyl group was substituted for methyl
and the latter compound 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
exhibited superior compatibility and performance in polyethylene compared
to the former.
In U.S. Pat. Nos. 4,283,327, 4,278,590 and 4,383,863 there is described
2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole which exhibits an
excellent combination of compatibility with and/or solubility in numerous
polymeric substrates along with superior resistance to loss from
stabilized compositions during high temperature processing or in end-use
applications where coatings or films of the stabilized compositions are
exposed even to ambient weathering and light exposures, and in
photographic applications. However,
2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole is still a solid
(melting point 105.degree.-106.degree. C.) which requires in many end-use
applications the concomitant use of a solvent or dispersing diluent to
allow for it to be used in practice. Such solvents or diluents are
undesired for reasons of cost and environmental and other considerations.
U.S. Pat. Nos. 3,983,132, 4,096,242 and 4,129,521 describe liquid mixtures
of 2-(2-hydroxy-5-nonylphenyl)-2H-benzotriazoles or of
2-(2-hydroxy-5-dodecylphenyl)-2H-benzotriazoles and stabilized
compositions using said mixtures where the nonyl or dodecyl groups each
represent an isomeric mixture of secondary and tertiary nonyl or dodecyl
groups attached to the para position relevant to the hydroxy group on the
2-phenyl moiety in the 2H-benzotriazole. The isomeric nonyl or dodecyl
groups are introduced into the phenol before it is coupled with the
2-nitrophenyldiazonium salt in a classic 2H-benzotriazole synthesis.
The instant liquid benzotriazoles differ from the benzotriazoles of these
three patents by the method by which they are prepared, by the location of
the branched alkyl group ortho to the hydroxy group and by in part the
nature of the branched alkyl group itself when prepared from a straight
chain alkene.
The liquid mixtures prepared by the method of U.S. Pat. No. 4,129,521 have
no substitution in the ortho position relevant to the hydroxy group thus
making said compounds prone to interaction with metal ions during resin
curing and in other end-use applications in polymer substrates and which
may lead to deleterious effects on color, light stability and ancillary
properties. The instant mixtures are substituted in the ortho position
relevant to the hydroxyl group and do not have this problem.
Certain hydrophobic non-diffusing hydroxyphenylbenzotriazoles are disclosed
as very useful as ultraviolet light absorbers in photographic gelatin
layers (U.S. Pat. No. 3,253,921). The instant benzotriazoles with their
liquid or non-crystalline nature, their desirable absorption
characteristics in the ultraviolet range and their photographic inertness
are particularly useful in photographic compositions, especially in
protecting color dye images against the harmful effects of ultraviolet
light.
U.S. Pat. No. 3,253,921 discloses benzotriazoles broadly, but does not
exemplify the instant benzotriazoles which are particularly effective in
stabilizing photographic compositions against the harmful effects of
ultraviolet radiation.
Further background in the area of stabilization of photographic dye images
is provided by U.S. Pat. No. 4,042,394 which describes the various
components in photographic compositions and the requirements for
stabilizing photographic dye images.
U.S. Pat. Nos. 4,383,863 and 4,447,511 describe the use of
2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole in photographic
elements and compositions. While this discrete benzotriazole exhibits
enhanced solubility in the various solvents and diluents used in
photographic elements, such solvents and diluents are still required since
said benzotriazole is still a crystalline solid.
The instant benzotriazole mixtures are liquid or non-crystalline leading to
the need for less or no solvent or diluent, thinner photographic layers
and all the concomitant economic benefits flowing therefrom.
U.S. Pat. No. 4,127,586 teaches that it is possible to alkylate phenols
with long chain olefins to get a phenol substituted with a mixture of
isomers as the alkyl substituents. The corresponding 2H-benzotriazole is
then prepared by the classic diazotizing, coupling and reduction route
starting with o-nitroaniline. The 2H-benzotriazole prepared by this
classic method differs in the distribution of isomeric components and in
chemical properties from the instant products made by an entirely
different process.
U.S. Pat. Nos. 4,587,346 and 4,675,352 pertain to the alkylation of
preformed 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole using a long
straight or branched alkene in the presence of an acid catalyst at
100.degree.-200.degree. C. Liquid mixtures are obtained by this process,
but the final products always contain a 5-methyl substituent. The instant
process and products differ from those of these two patents. The 5-methyl
group is unaffected by the process conditions used neither being
displaced, rearranged or disproportionated during the alkylation process
of said patents.
The instant process and products differ markedly from this situation since
the higher alkyl groups on the 3 and/or 5-positions can be displaced,
rearranged, dealkylated or fragmented during the instant process giving a
quite different melange of useful products from the preformed starting
2H-benzotriazoles and the liquid products of the prior art.
DETAILED DISCLOSURE
This invention pertains to selected liquid or non-crystalline
2-aryl-2H-benzotriazole light absorbers and to organic materials, both
polymeric and non-polymeric, stabilized thereby, as well as to
photographic elements containing said liquid materials. The stabilized
compositions include plastics, coatings, fibers, films, and photographic
substrates.
Another object of this invention is the process for preparing said liquid
or non-crystalline mixtures of benzotriazoles. These liquid mixtures
exhibit great resistance to volatilization, enhanced solubility in
selected solvents, desirable absorption characteristics in the ultraviolet
range and photographic inertness. This combination of properties makes
these benzotriazoles particularly useful in photographic compositions
especially in protecting color dye images against the harmful effects of
ultraviolet light.
More particularly, the instant invention pertains to a normally liquid or
non-crystalline mixture of benzotriazoles, suitable for stabilizing
organic materials against light-induced deterioration, which consists
essentially of compounds of the formula
##STR1##
wherein T.sub.1 is hydrogen, chloro, alkyl of 1 to 4 carbon atoms or
alkoxy of 1 to 4 carbon atoms, and
where one of T.sub.2 or T.sub.3 is a random of at least three isomeric
alkyl groups each having 8 to 40 carbon atoms, and
the other of T.sub.2 or T.sub.3 is hydrogen or methyl, and
where one of T.sub.2 or T.sub.3 is a random statistical mixture as defined
above and the other of T.sub.2 or T.sub.3 is alkyl of 2 to 12 carbon
atoms, cycloalkyl of 5 to 8 carbon atoms or aralkyl of 7 to 9 carbon
atoms; and
in minor proportions compounds where both of T.sub.2 and T.sub.3 are a
random statistical mixture as defined above or where the compounds
represent dealkylated or fragmented-alkyl substituted products of the
benzotriazoles of formula I
which mixture is prepared by reacting a 2H-benzotriazole of formula (A) or
(B)
##STR2##
where R.sub.1 is hydrogen, chloro, alkyl of 1 to 4 carbon atoms or alkoxy
of 1 to 4 carbon atoms,
R.sub.2 is alkyl of 2 to 12 carbon atoms, cycloalkyl of 5 to 8 carbon atoms
or aralkyl of 7 to 9 carbon atoms,
G.sub.1 has the same meaning as R.sub.1, and
G.sub.2 and G.sub.3 are independently branched alkyl of 3 to 12 carbon
atoms, cycloalkyl of 5 to 8 carbon atoms or aralkyl of 7 to 9 carbon
atoms, or one of G.sub.2 and G.sub.3 is methyl or ethyl when the other of
G.sub.2 and G.sub.3 is branched alkyl, cycloalkyl or aralkyl as defined
above,
with a straight or branched chain alkene of 8 to 40 carbon atoms or mixture
of said alkenes in the presence of an acidic catalyst at a temperature of
100.degree. to 200.degree. C.
Preferably T.sub.1, R.sub.1 and G.sub.1 are hydrogen or chloro; most
preferably hydrogen.
Preferably T.sub.2 or T.sub.3 in the random statistical mixture of alkyl
groups is alkyl of 8 to 16 carbon atoms; most preferably alkyl of 10 to 12
carbon atoms.
Preferably when T.sub.2 or T.sub.3 is not the random statistical mixture of
alkyl groups, T.sub.2 or T.sub.3 is hydrogen, branched alkyl of 4 to 8
carbon atoms or alpha,alpha-dimethylbenzyl, but T.sub.2 and T.sub.3 are
not both hydrogen at the same time.
Preferably R.sub.2 or G.sub.2 and G.sub.3 are independently branched alkyl
of 3 to 12 carbon atoms or aralkyl of 7 to 9 carbon atoms, or R.sub.2 or
one of G.sub.2 or G.sub.3 is methyl or ethyl and the other of G.sub.2 or
G.sub.3 is branched alkyl of 3 to 12 carbon atoms.
When R.sub.2, G.sub.2 or G.sub.3 is branched alkyl of 3 to 12 carbon atoms,
said alkyl is for example isopropyl, sec-butyl, tert-butyl, tert-amyl,
tert-octyl or tert-dodecyl. When R.sub.2, G.sub.2 or G.sub.3 is aralkyl of
7 to 9 carbon atoms, said aralkyl is benzyl, alpha-methylbenzyl or
alpha,alpha-dimethylbenzyl.
The 2-(2-hydroxyphenyl)-2H-benzotriazole light absorbers are conventionally
obtained by coupling an appropriately substituted phenol with an
o-nitrophenyl diazonium salt to prepare an o-nitroazobenzene intermediate
which is subsequently reduced and cyclized to the corresponding
2H-benzotriazole.
It is clear that any change in the nature of the substitution on the phenol
moiety, for example for the purpose of modifying final 2H-benzotriazole
properties, must be carried out on the phenol molecule itself before the
conventional 2H-benzotriazole synthesis is begun. This requires one or
more additional steps in the synthetic sequence for each new
2H-benzotriazole product. Moreover, unavoidable side reactions occur
during these steps which make it necessary to include at least one
crystallization step in order to obtain a product of acceptable purity.
The above procedure is poorly adapted for the preparation of
non-crystalline or liquid products where purification by crystallization
is not possible.
Indeed the process described in U.S. Pat. No. 4,129,521 discloses that, in
order to obtain liquid products of acceptable purity, it is necessary to
(1) vacuum distill the crude 2H-benzotriazole product, treat the once
distilled product with acetic anhydride to remove various undesirable
impurities; carry out a second vacuum distillation on the acetylated
mixture; blow the distillate with air at elevated temperature for many
hours and finally distill the material for a third time under molecular
distillation conditions. Only then after these laborious and economically
unattractive procedures is a liquid product useful as a light absorber
obtained.
Clearly a better method of making liquid or non-crystalline
2H-benzotriazoles was needed since the conventional approach of preparing
an alkylated phenol and then the benzotriazole from said phenol involves
an almost impossible task of removing undesirable impurities from the
benzotriazole in a practical manner.
The approach of alkylating a preformed 2H-benzotriazole was not believed
promising since it was known that phenols substituted in the ortho
position by a 2H-benzotriazolyl moiety are vastly deactivated in respect
to electrophilic substitution (= alkylation) on the phenolic ring.
It was thus surprising that direct alkylation on the phenolic ring of
preformed 2H-benzotriazoles could be carried out to give the desired mixed
alkylated products in a facile and direct manner.
As described in U.S. Pat. Nos. 4,587,346 and 4,675,352, the direct
alkylation of 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole with an
alpha-olefin or straight chain alkene; or with a branched alkene occurred
in excellent conversions (over 90%) of the preformed benzotriazole to
alkylated products.
Since the 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole is already
substituted in the para position to the hydroxyl group, alkylation is
perforce directed to the ortho position to the hydroxyl moiety to obtain a
mixture of 2-(2-hydroxy-3-higher branched
alkyl-5-methylphenyl)-2H-benzotriazoles.
The nature of the random statistical mixture of alkyl groups that are
inserted into the 2H-benzotriazoles of formula I as T.sub.2 or T.sub.3
depends on which type of alkene is used for the alkylation.
The use of an alpha-olefin or straight chain alkene leads to the insertion
of branched secondary alkyl groups while the use of a branched alkene
leads to branched alkyl groups having a multiplicity of alkyl branches
along the main alkyl chain.
The 2H-benzotriazoles used as starting materials in the instant invention
differ significantly from the
2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole used in the prior art
process.
Whereas the methyl group in the 5-position of 2-(2-hydroxy-5
methylphenyl)-2H-benzotriazole is not labile, is not displacable and
cannot be fragmented, alkylation in the prior art process is perforce
directed solely to the unsubstituted ortho position to the hydroxyl
moiety.
This is not the case with the instant 2H-benzotriazole which fall into two
categories (A) and (B):
##STR3##
wherein R.sub.1 is hydrogen, chloro, alkyl of 1 to 4 carbon atoms or
alkoxy of 1 to 4 carbon atoms,
R.sub.2 is alkyl of 2 to 12 carbon atoms, cycloalkyl of to 8 carbon atoms
or aralkyl of 7 to 9 carbon atoms,
G.sub.1 has the same meaning as R.sub.1, and
G.sub.2 and G.sub.3 are independently a branched alkyl of 3 to 12 carbon
atoms, cycloalkyl of 5 to 8 carbon atoms or aralkyl of 7 to 9 carbon
atoms, or one of G.sub.2 and G.sub.3 is methyl or ethyl when the other of
G.sub.2 or G.sub.3 is branched alkyl, cycloalkyl or aralkyl as defined
above.
More particularly, the instant process is a process for preparing a
normally liquid or non-crystalline mixture of benzotriazoles, suitable for
stabilizing organic materials against light induced deterioration, which
consists essentially of the formula
##STR4##
wherein T.sub.1 is hydrogen, chloro, alkyl of 1 to 4 carbon atoms or
alkoxy of 1 to 4 carbon atoms, and
in major proportions compounds
where one of T.sub.2 or T.sub.3 is a random statistical mixture of at least
three isomeric alkyl groups each having 8 to 40 carbon atoms, and
the other of T.sub.2 or T.sub.3 is hydrogen or methyl, and
where one of T.sub.2 or T.sub.3 is a random statistical mixture as defined
above and the other of T.sub.2 or T.sub.3 is alkyl of 2 to 12 carbon
atoms, cycloalkyl of 5 to 8 carbon atoms or aralkyl of 7 to 9 carbon
atoms; and
in minor proportions compounds where both of T.sub.2 and T.sub.3 are a
random statistical mixture as defined above or where the compounds
represent dealkylated or fragmented-alkyl substituted products of the
benzotriazoles of formula I
which process comprises
reacting a 2H-benzotriazole of the formula (A) or (B)
##STR5##
wherein R.sub.1 is hydrogen, chloro, alkyl of 1 to 4 carbon atoms or
alkoxy of 1 to 4 carbon atoms,
R.sub.2 is alkyl of 2 to 12 carbon cycloalkyl of 5 to 8 carbon atoms or
aralkyl of 7 to 9 carbon atoms,
G.sub.1 has the same meaning as R.sub.1, and
G.sub.2 and G.sub.3 are independently branched alkyl of 3 to 12 carbon
atoms, cycloalkyl of 5 to 8 carbon atoms or aralkyl of 7 to 9 carbon
atoms, or one of G.sub.2 and G.sub.3 is methyl or ethyl when the other of
G.sub.2 and G.sub.3 is branched alkyl, cycloalkyl or aralkyl as defined
above,
with a straight or branched chain alkene of 8 to 40 carbon atoms or mixture
of said alkenes in the presence of an acidic catalyst at a temperature of
100.degree. to 200.degree. C.
Under these vigorous reaction conditions the alkylating agent (the alkene,
straight or branched chain) itself undergoes a chemical transformation or
isomerization. Accordingly the alkyl substituents introduced into the
benzotriazole are not a single discrete moiety, but rather a random
statistical mixture of isomeric groups. This random statistical mixture of
groups (T.sub.2 or T.sub.3) represents a structural diversity which
contributes to the liquid and non-crystalline physical state of the
resulting products.
Under the instant process conditions the double bond in the alkene
alkylating agent is isomerized along the carbon chain to give a random
statistical mixture of moieties which can then be attached to the phenolic
ring in the benzotriazole.
Illustrating with the alpha-olefin 1-octene, the random statistical mixture
of octyl groups which would be included as T.sub.2 or T.sub.3 when T.sub.2
or T.sub.3 is octyl are
##STR6##
Thus T.sub.2 or T.sub.3 as octyl would lead to at least three isomers
present in the mixture of benzotriazoles prepared.
Indeed, under the instant process conditions, the alkene being used in the
instant process may fragment, dimerize or recombine in some fashion before
reacting with the 2H-benzotriazole starting material. Such possibilities
may in part account for the wide mixture of molecular species noted in the
working Examples 1-11 where mass spectrographic analysis shows the
presence of inter alia species with alkyl substituents having twice the
number of carbon atoms as were present in the original alkene being used.
In like manner, mass spectrographic anaylysis indicated some species with
alkyl substituents having less than the number of carbon atoms in the
alkene being used in the instant process or even having less than the
number of carbon atoms in the alkyl groups in the original 2H-benzotriazle
starting material used. In some cases, there were species having no alkyl
substituents at all with complete dealkylation of the original
2H-benzotriazole having occurred. Inspection of the mass spectrographic
analysis data shows that the combined amounts of all of these possible
species enumerated in this paragraph are essentially minor components in
the instant mixtures.
Although clearly the alkyl groups present in the instant mixtures are in an
overwhelming degree present at the 3- and 5-positions (ortho and para
positions) of the phenolic ring in the 2H-benzotriazoles of formula I, it
cannot be ruled out that some substitution at the meta (4-) position or
even in the benzo ring may not also occur in very minor and
inconsequential amounts.
In the case where the starting 2H-benzotriazole has a lower alkyl
substituent on the benzo ring as R.sub.1 or G.sub.1, said alkyl
substituent is also unlikely to participate in the instant process since
said benzo ring is quite deactivated and is not prone to direct alkylation
and to participation in the instant process.
The alkenes useful in the instant process are any alkene whether straight
or branched chain including alpha-olefins and alkenes having an internal
double bond. During the instant alkylation process the double bond is
isomerized along the carbon chain to give a random statistical mixture of
alkenes which in turn produce for T.sub.2 and T.sub.3 a random statistical
mixture of alkyl substituents.
Further contributing to the random statistical nature of the alkyl
substituents for T.sub.2 and T.sub.3 is the fact that commercially
available alkenes are often mixture of alkenes.
The preferred alkenes useful in the instant process are the alpha-olefins.
The alpha-olefins useful in this process are for example 1-octene,
1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene or
1-triacontene.
These alpha-olefins are largely items of commerce or are made by the
telomerization of ethylene by known methods.
Straight chain alkenes containing an internal double bond may be for
example 2-octene, 4-octene, 5-decene or 9-tricosene.
These alkenes are also largely items of commerce.
The branched chain alkenes useful in this process are for example
dipropylene, tripropylene, tetrapropylene, pentapropylene, diisobutylene,
triisobutylene, tetraisobutylene, pentaisobutylene,
2,2,4,6,6-pentamethyl-3-heptene, diisoamylene, triisoamylene,
tetraisoamylene or pentaisoamylene.
These highly branched alkenes are largely items of commerce or can be
prepared from propylene, isobutylene or isoamylene by oligomerization with
acid catalysts.
That this mixture of isomeric radicals as T.sub.2 or T.sub.3 is critical to
obtaining a liquid or non-crystalline product may be seen from the fact
that, when the alkyl substitution is a specific isomer, solid crystalline
products are obtained. For example,
2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole melts at
105.degree.-106.degree. C.
The alkylation processes can be carried out over a range of conditions of
time, temperature, olefin to benzotriazole ratios, catalysts and catalyst
concentrations.
Sufficient time must be allowed for the alkylation to occur usually about 4
hours, but reaction times in excess of 12 hours do not increase yield of
alkylated product. Preferably the alkylation reaction is carried out for a
6- to 8- hour period.
Relatively vigorous reaction conditions are needed since even the phenolic
ring of the starting 2H-benzotriazole is deactivated. Reaction
temperatures of 100.degree. to 200.degree. C. may be used. Temperatures
below 140.degree. C. give lower yields of alkylated product and
temperatures in excess of 180.degree. C. produce products of lesser
quality and in lower yields. Preferably the process is carried out at
140.degree. to 170.degree. C., and most preferably at
160.degree.-165.degree. C. where yields in excess of 90% are obtained.
In order to alkylate the 2H-benzotriazole there must be at least 1
equivalent of alkene per equivalent of 2H-benzotriazole. Since competing
reactions are also possible under these reactions conditions in respect to
the alkene, such as dimerization, oligomerization or polymerization,
yields of desired alkylated product are usually less than 40% when a 1:1
equivalent ratio of alkene:benzotriazole is used.
Increasing the concentration of alkene in respect to benzotriazole to a 4:1
equivalent ratio greatly increases yields of alkylated products to over
85%.
Larger excesses of alkene at a 6:1 equivalent ratio do not increase yields
further.
Preferably the equivalent ratio of alkene:benzotriazole in the instant
processes is 3.5 to 4.5:1.
The acidic catalyst is selected from the group consisting of aliphatic,
aromatic and substituted aromatic sulfonic acids, sulfuric acid,
phosphoric acid, acidic clays and heterogenous acidic catalysts (molecular
sieves).
The concentration of catalyst useful in the instant process is 0.2 to 3
equivalents of catalyst per equivalent by benzotriazole, preferably 0.3 to
2 equivalents, and most preferably 0.5 to 1 equivalent of acid catalyst
per equivalent of benzotriazole.
Examples of useful sulfonic acids are methanesulfonic acid, ethanesulfonic
acid, butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid and
dodecylbenzenesulfonic acid. Aliphatic sulfonic acids are preferable.
Commercially available acid activated clays such as Filtrol XJ-8303;
Filtrol XJ-8405; Filtrol 22; Filtrol 4; and Filtrol 13 are also effective
alkylation catalysts in the instant processes.
The most preferred catalyst is methanesulfonic acid.
The instant mixtures of formula I may be isolated following the alkylation
reaction by a number of methods including the extraction procedures
described in U.S. Pat. Nos. 4,587,346 and 4,675,352. Another facile method
involves vacuum distillation at reduced pressure. The instant mixtures are
usually distilled at temperatures in the range of 180.degree.-210.degree.
C. at about 0.05 mm Hg.
Protection against damage caused by UV light is particularly important in
photographic technology and especially in color photographic technology.
In order to protect the components (in particular dyes and couplers)
present in a color photographic material as effectively as possible
against destruction by ultraviolet light, UV absorbers are normally
inserted into one or more of the upper layers of the material. This is
effected as a rule by dissolving the UV-absorber in a high-boiling solvent
and dispersing this solution, in the form of very fine droplets, in the
appropriate coating solution. Since these droplets have a disadvantageous
effect on the mechanical properties of the layer, and can "exude" if they
are in the top layer of the material, it is important to keep the quantity
of absorber solution as small as possible. This also makes it possible to
produce thinner layers, which, in turn, offers advantages in processing
(carry-over between baths and drying). It is therefore desirable to employ
UV-absorbers which have as high a solubility as possible in the customary
high-boiling solvents. The UV-absorbers of the state of the art, for
example the stabilizers disclosed in Japanese Application Sho 54-95,233 do
not, to a satisfactory extent, fulfil this requirement.
It has now been found that the instant products being liquid or
non-crystalline can be used in color photographic material without the
concomitant use of high-boiling solvents or with a very minimum amount
thereof. Moreover, the instant compounds are essentially non-volatile and
do not exude.
A typical photographic composition comprises a paper support on which are
coated one or more light-sensitive layers and a layer containing the
ultraviolet light absorber in a binder so placed as to protect the layer
or layers requiring protection.
It is known that ultraviolet radiation has a detrimental effect on
photographic layers. Ultraviolet radiation in light sources used for
exposure of photographic products sometimes produces undesired exposure of
the layer or layers of a photographic element. This is especially true in
photographic elements designed for use in color photography in which the
emulsion has been sensitized to the longer wavelength regions and it is
desirable to record only the rays of the visible spectrum.
Color photographs on multilayer photographic material, particularly those
in which the dye images are formed in sensitive emulsion layers by color
development, are susceptible to fading and discoloration by the action of
ultraviolet radiation to which the photographs are subjected during
viewing. The residual couplers contained in the emulsion layer after the
formulation of the picture images may be attacked by ultraviolet radiation
resulting in an undersirable stain in the finished photograph. The action
of ultraviolet radiation on finished color photographs is particularly
noticeable on positive prints on paper or other opaque support since this
type of print is frequently viewed in daylight which has a high content of
ultraviolet radiation. The dye-fading and discoloration effects appear to
be caused primarily by those wavelengths of light close to the visual
region of the spectrum, i.e., 300-400 nm.
It is known that silver halide photographic materials can be protected from
ultraviolet radiation by incorporating nondiffusing ultraviolet absorbing
compounds in the silver halide emulsion layers or in overlying colloid
coatings.
A large number of ultraviolet absorbers have been proposed for this use.
Ultraviolet absorbing compounds for photographic use must generally be
colorless or nearly colorless, show good compatability with the medium in
which they are incorporated, be inert to other photographic addenda in the
element and in the processing solution, must have good ultraviolet
absorptivity and be stable to ultraviolet radiation. Representative
compounds for incorporation in photographic elements are described for
example, in U.S. Pat. No. 3,253,921.
Aromatic organic compounds such as ultraviolet absorbers, dye-forming
couplers, antistain agents, filter dyes and the like to be effective must
be nondiffusing and adequately distributed in highly dispersed form in the
aqueous photographic gelatin layers.
This can be accomplished by a variety of chemical or physical techniques
including the substitution of sulfonic acid or other solubilizing groups
on the organic molecule; by use of a polar organic solvent imbibition
procedures; or by solvent dispersion techniques.
The instant liquid or non-crystalline 2H-benzotriazoles are extremely
useful as ultraviolet absorbers in photographic gelatin layers. They
exhibit desirable absorption characteristics in the ultraviolet region,
i.e., maximum absorption in the near ultraviolet and sharp cut-off just
outside the visible region, are essentially colorless, are readily
dispersed or dissolved by either the solvent-dispersion or imbibition
methods, and are photographically inert.
The instant compounds exhibit excellent compatibility characteristics in
the gelatin layers of the photographic composition which lead to
compositions essentially without haze coupled with superior protection of
the color dye images against the harmful effects of ultraviolet radiation.
This combination of properties clearly distinguishes the instant
benzotriazole light absorbers from the generic disclosure of U.S. Pat. No.
3,253,921. These salubrious results are obtained when the instant
benzotriazoles are incorporated directly into the gelatin layer or by the
solvent dispersion technique.
An object of the invention is to provide novel photographic elements
protected against the harmful effects of ultraviolet radiation by
incorporation of ultraviolet absorbing materials. Another object is to
provide photographic color materials containing ultraviolet absorbers
incorporated in a highly stable form. A further object is to provide a
non-diffusing ultraviolet absorber.
The invention relates further to stabilized organic material which is in
the form of photographic material or is part of a photographic material,
the photographic material containing, preferably in top layers, 0.05 to 5%
by weight, relative to the photographic material without stabilizer, of a
compound according to the invention.
When the instant compounds are liquid, the instant benzotriazoles are
incorporated into a hydrophilic colloid by heating an aqueous solution of
said hydrophilic colloid containing the liquid benzotriazole and an
appropriate dispersing agent to a moderate temperature above the easy flow
point of the instant benzotriazole, agitating the resulting mixture to
obtain a fine dispersion of the benzotriazole in the colloid, and then
cooling the mixture.
When the instant compounds are not liquid at room temperature, but are
non-crystalline, the use of a minimum amount of high-boiling solvent to
assist in getting the instant compound to flow is contemplated to achieve
the above objects by the solvent dispersion technique to incorporate the
instant compounds in aqueous hydrophilic colloid solutions for coating
silver halide emulsion layers or associated hydrophilic colloid layers.
The preferred high-boiling solvents include di-n-butyl phthalate, benzyl
phthalate, triphenyl phosphate, tri-o-cresyl phosphate, diphenyl
mono-p-tert-butylphenyl phosphate, monophenyl di-p-tert-butylphenyl
phosphate, diphenyl mono-o-chlorophenyl phosphate, monophenyl
di-o-chlorophenyl phosphate, tri-p-tert-butylphenyl phosphate,
tri-o-phenylphenyl phosphate, di-p-tert-butylphenyl mono(5-tert-butyl-2-
phenylphenyl) phosphate, etc.
The hydrophilic colloids or binders advantageously include gelatin,
albumin, etc., cellulose derivatives, polyvinyl compounds, etc. The
polymeric binders include polyvinyl alcohol or a hydrolyzed polyvinyl
acetate; a far hydrolyzed cellulose ester such as cellulose acetate
hydrolyzed to an acetyl content of 19-26 percent; a water-soluble
ethanolamine cellulose acetate, a polyacrylamide having a combined
acrylamide content of 30-60 percent and a specific viscosity of 0.25-1.5
or an imidized polyacrylamide of like acrylamide content and viscosity; a
vinyl alcohol polymer containing urethane carboxylic acid groups; or
containing cyanoacetyl groups such as the vinyl alcohol/vinyl cyanoacetate
copolymer; or a polymeric material which results from polymerizing a
protein or a saturated acylated protein with a monomer having a vinyl
group.
The dispersion of an instant compound in the binder material is coated over
the light-sensitive layer of the photographic element. Where the
photographic element is a material intended for use in color photography,
the ultraviolet filter layer need not be an outer layer, but can be used
as an interlayer, i.e., under the layer or layers not needing the
protection and over the layer or layers needing protection. For example,
in a multilayer material comprising three differentially sensitized
layers, the red-sensitive layer being adjacent to the support, the
green-sensitive layer being superimposed on the red-sensitive layer and
the blue-sensitive layer being outermost with respect to the other
light-sensitive layers, the ultraviolet filter layer can be placed between
the blue and green-sensitive layers or between the green and red-sensitive
layers. Similarly, in another photographic element in which the layers are
reversed, that is, the blue-sensitive layer is coated over the support,
and the green and red-sensitive layers are superposed over the
blue-sensitive layer in that order, the ultraviolet filter layer can be
over all three layers or between any two of the layers. Alternatively, the
ultraviolet absorbing composition can be incorporated directly in the
light-sensitive emulsion instead of, or in addition, being present in
another layer. The amount of the ultraviolet absorbing material used can
be varied, depending upon the effect desired and the use that will be made
of the material.
The ultraviolet absorbing compositions are coated over a wide range of
concentrations; usually they are coated in the range of from 20 to 300 mg.
of ultraviolet absorbing compound per ft..sup.2 photographic element. A
preferred range is from 75 to 160 mg/ft..sup.2. The optimum coating
concentrations will depend upon the particular photographic element to be
protected and the amount of protection desired. The optimum coating
concentrations for a given photographic element can be determined by
methods well known in the art.
Any photographic element may be advantageously protected according to the
invention. These photographic elements may have as their support any of
the conventional support materials, such as firm supports, e.g., cellulose
acetate, etc. opaque supports, such as white pigmented film, paper and the
like.
The instant ultraviolet absorbing compounds are characterized by their
non-diffusibility in coated layers, good stability in the incorporating
solvents and their good ultraviolet absorption. Ultraviolet absorbing
layers containing the instant compounds incorporated according to the
preferred methods of the invention have unexpectedly excellent stability
upon prolonged exposure to ultraviolet radiation which makes them ideally
suited for protecting photographic elements, particularly dye images in
color materials.
The instant liquid benzotriazoles may be used advantageously in
photographic elements with other liquid ultraviolet absorbers (UVA) such
as 5-chloro-2-[2-hydroxy-3-tert-butyl-5-(2-octyloxyethyl)-phenyl]-2H-benzo
triazole.
The instant liquid benzotriazoles are also useful as solvents for other
solid UVA materials or for other components in a silver halide
photographic element when used alone or in combination with common
photographic oils as described in European Pat. Application Nos. 84,692
and 84,694.
Such other components include
yellow, magenta and cyan couplers
DIR couplers, black couplers, colorless couplers
chromogenic coupler stabilizers
chromogenic dye stabilizers
accutance dyes, antihalation dyes, dye-bleach dyes
formaldehyde scavengers
sensitizing dyes
optical brightening agents
oxidized developer scavengers
compounds which release diffuseable dyes on development
electron transfer agents
Examples of other UVA materials which may be used in combination with the
instant compounds include
1. Benzophenones
2,4-dihydroxy-benzophenone
2-hydroxy-4-ethoxy-benzophenone
2,2'-dihydroxy-4-methoxy-benzophenones
2-hydroxy-4-n-octoxy-benzophenone
2-hydroxy-4-isooctoxy-benzophenone
2-hydroxy-4-dodecyloxy-benzophenone
2. Benzotriazoles
2-(2-hydroxy-5-methylphenyl)-benzotriazole,
2-(2-hydroxy-3,5-di-t-butylphenyl)-benzotriazole,
2-(2-hydroxy-3-t-butyl-5-ethylphenyl)-5-chlorobenzotriazole,
2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole,
2-(2-hydroxy-3,5-di-tert-amylphenyl)-benzotriazole,
2-(2-hydroxy-3-s-butyl-5-t-butylphenyl)-benzotriazole,
2-(2-hydroxy-5-t-butylphenyl)-benzotriazole,
2-(2-hydroxy-5-t-octylphenyl)-benzotriazole, a mixture of 50% of
2-[(2-hydroxy-3-t-butyl-5-((2"-n-octoxy-carbonyl)-ethyl)phenyl]-5-chlorobe
nzotriazole and 50% of
2-[(2-hydroxy-3-t-butyl-5-((2"-ethylhexyloxy)carbonyl)ethyl)phenyl]-5-chlo
robenzotriazole,
2-[2-hydroxy-3,5-di-(alpha,alpha-dimethylbenzyl)phenyl]-benzotriazole
3. Benzylidene malonates
methyl 2-carboxymethyl-3-(4'-methoxyphenyl)-acrylate
4. Salicylates
p-octylphenyl salicylate
phenyl salicylate
t-butylphenyl salicylate
5. Monobenzoates
Resorcinol monobenzoate
3,5-di-t-butyl-4-hydroxybenzoic acid
hexadecyl ester
6. Oxamides
5-t-butyl-2-ethoxy-2'2'-ethyloxanilide,
2-ethoxy-2'-ethyloxanilide
7. 5-dialkylamino-2,4-pentadienoic acid esters
5-diethylamino-2-phenylsulphonyl-2,4-pentadienoic acid hendecylester
8. 5-dialkylamino-2-cyano-2,4-pentadiene nitriles
5-dihexylamino-2-cyano-2,4-pentadiene nitrile
9. 2,4-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate,
3,5-ditertieary-butyl-p-hydroxy-benzoic acid,
di(1,2,2,6,6-pentamethyl-4-piperidinyl)-butyl
(3',5'-di-t-butyl-4-hydroxybenzyl)malonate,
bis(1,2,6,6-tetramethyl-4-piperidinyl) sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,
butane tetracarboxylic acid tetra(2,2,6,6-tetramethyl-4-piperidinyl)ester
The instant compounds may also be used in cyan layers together with either
phenol, naphthol or 2,5-diacylaminophenol couplers or mixtures of these
couplers to prevent image fading and discoloration.
The use of known benzotriazoles in such systems is described in Japanese
Kokai Sho 58-221,844 and 59-46,646.
The compounds of this invention are effective light stabilizers in a wide
range of organic polymers. Polymers which can be stabilized include:
1. Polymers which are derived from mono- or diolefins e.g., polyethylene
which can optionally be crosslinked, polypropylene, polyisobutylene,
polymethylbutene-1, polymethylpentene-1, polyisoprene, polybutadiene.
2. Mixtures of the homopolymers cited under 1), for example mixtures of
polypropylene and polyethylene, polypropylene and polybutene-1,
polypropylene and polyisobutylene,
3. Copolymers of the monomers based on the homopolymers cited under 1), for
example ethylene/propylene copolymers, propylene/butene-1 copolymers,
propylene/iso-butylene copolymers, ethylene/butene-1 copolymers as well as
terpolymers of ethylene and propylene with a diene, for example hexadiene,
dicyclopentadiene or ethylidene norbornene, and copolymers of
alpha-olefins, e.g., ethylene with acrylic or methacrylic acid, and blends
of such copolymers with homopolymers described in paragraphsl and 2 above.
4. Polystyrene.
5. Copolymers of styrene and of alpha-methylstyrene, for example
styrene/butadiene copolymers, styrene/acrylonitrile copolymers,
styrene/acrylonitrile/methacrylate copolymers, styrene/acrylonitrile
copolymers modified with acrylic ester polymers to provide impact strength
as well a block copolymers, e.g., styrene/butadiene/styrene,
styrene/isoprene/styrene and styrene/ethylenepropylene/ styrene block
copolymers.
6. Graft copolymer of styrene, for example the graft polymer of tyrene to
polybutadiene, the graft polymer of styrene with acrylonitrile to
polybutadiene as well as mixtures thereof with the copolymers cited under
5), commonly referred to as acrylonitrile/butadiene/styrene or ABS
plastics.
7. Halogen-containing vinyl polymers, for example polyvinyl chloride,
polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated
rubbers, vinyl chloride/vinylidene chloride copolymers, vinyl
chloride/vinyl acetate copolymers, vinylidene chloride/vinyl acetate
copolymers.
8. Linear and crosslinked polymers which are derived from
alpha,beta-unsaturated acids and derivatives thereof, such as amides and
polyacrylonitrile.
9. Polymers which are derived from unsaturated alcohols and amines and from
the acyl derivatives thereof or acetals, for example polyvinyl alcohol,
polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl
maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine and
copolymers thereof with other vinyl compounds, for example ethylene/vinyl
acetate copolymers.
10. Hompolymers and copolymers which are derived from epoxides, for example
polyethylene oxide or the polymers which are derived from bis-glycidyl
ethers.
11. Polyacetals, for example polyoxymethylene, as well as polyoxymethylenes
which contain ethylene oxide as comonomer.
12. Polyalkylene oxides, for example polyoxyethylene, polypropylene oxide
or polybutylene oxide.
13. Polyphenylene oxides, and blends of polyphenylene oxides with impact
resistant polystyrene.
14. Polyurethanes and polyureas, such as in urethane coatings.
15. Polycarbonates.
16. Polysulfones.
17. Polyamides and copolyamides which are derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the corresponding
lactams, for example polyamide 6, polyamide 6/6, polyamide 6/10, polyamide
11, polyamide 12, poly-m-phenylene-isophthalamide.
18. Polyesters which are derived from dicarboxylic acids and dialcohols
and/or from hydroxycarboxylic acids or the corresponding lactones, for
example polyethylene glycol terephthalate, poly-1,4-dimethylol-cyclohexane
terephthalate.
19. Cross-linked polymers which are derived from aldehydes on the one hand
and from phenols, ureas and melamine on the other, for example
phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resin.
20. Alkyd resins, for example glycerol/phthalic acid resins and mixtures
thereof with melamine/formaldehyde resins.
21. Unsaturated polyesters reins which are derived from copolyesters of
saturated and unsaturated dicarboxylic acids with polyhydric alcohols as
well as from vinyl compounds as cross-linking agents and also the
halogen-containing, flame-resistant modifications thereof.
22. Natural polymers, for example cellulose, rubber, as well as the
chemically modified homologous derivatives thereof, for example cellulose
acetates, cellulose propionates and cellulose butyrates and the cellulose
ethers, for example methyl cellulose.
The stabilizing of polyolefins, styrene polymers, polyacrylates,
polyamides, polyurethanes, halogen containing vinyl polymers, alkyd
resins, thermoset acrylic resins, and epoxy resins is of particular
importance, and the instant benzotriazole mixtures are outstandingly
suitable for this purpose. Examples of such polymers are high density and
low density polyethylene, polypropylene, ethylene/propylene copolymers,
polystyrene, styrene block copolymers, halogen containing vinyl polymers,
linear (=thermoplastic) and crosslinked (=thermoset) polyacrylates and
polyurethanes, alkyd resins and epoxy resins in the form of coatings,
lacquers, filaments, films, sheets, adhesives, elastomers, foams or shaped
articles.
The instant stabilizers are added to the substrates in a concentration of
0.05 to 10% by weight, calculated relative to the material to be
stabilized. Preferably, 0.1 to 5% by weight of the stabilizer calculated
relative to the material to be stabilized, is incorporated into the
latter.
Incorporation can be effected after polymerization, for example by mixing
the compounds and, if desired, further additives into the melt by the
methods customary in the art, before or during shaping, or by applying the
dissolved or dispersed compounds to the polymer, with subsequent
evaporation of the solvent if necessary.
The stabilizers can also be added to the substrates to be stabilized in the
form of a master batch which contains these compounds, for example in a
concentration of 2.5 to 25% by weight.
Although the compounds of the invention may be used to provide a light
stabilizing function, the compounds of this invention are often combined
with other stabilizers, even other light stabilizers, in the preparation
of stabilized compositions. The stabilizers may be used with phenolic
antioxidants, pigments, colorants or dyes, light stabilizers such as
hindered amines, metal deactivators, etc.
In general, the stabilizers of this invention are employed from about 0.05
to about 10% by weight of the stabilized composition, although this will
vary with the particular substrate and application. An advantageous range
is from about 0.1 to about 5%.
The stabilizers of Formula I or II may readily be incorporated into the
organic substrates by conventional techniques, at any convenient stage
prior to the manufacture of shaped articles therefrom. For example, the
stabilizer may be mixed with the dry polymer, or a suspension, solution or
emulsion of the stabilizer may be mixed with a solution, suspension, or
emulsion of the polymer. The stabilized polymer compositions of the
invention may optionally also contain from about 0.05 to about 10%,
preferably from about 0.1 to about 5%, by weight of various conventional
additives, such as the following, particularly phenolic antioxidants or
light-stabilizers, or mixtures thereof:
1 Antioxidants
1.1 Simple 2,6-dialkylphenols, such as, for example,
2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-di-methylphenol,
2,6-di-tert.-butyl-4-methoxymethylphenol and
2,6-dioctadecyl-4-methylphenol.
1.2 Derivatives of alkylated hydroquinones, such as for example,
2,5-di-tert.-butyl-hydroquinone, 2,5-di-tert.-amyl-hydroquinone,
2,6-di-tert.-butyl-hydroquinone, 2,5-di-tert.-butyl-4-hydroxy-anisole,
3,5-di-tert.-butyl-4-hydroxy-anisole, 3,5-di-tert.-butyl-4-hydroxyphenyl
stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.
1.3 Hydroxylated thiodiphenyl ethers, such as for example,
2,2'-thio-bis-(6-tert.-butyl-4-methylphenol),
2,2'-thio-bis-(4-octylphenol),
4,4'-thio-bis-(tert.-butyl-33-methylphenol), 4,4'-thio-bis-(3,6-di-sec.-am
ylphenol), 4,4'-thio-bis-(6-tert.-butyl-2-methylphenol) and
4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.
1.4 Alkylidene-bisphenols, such as, for example,
2,2'-methylene-bis-(6-tert.-butyl-4-methylphenol),
2,2'-methylene-bis-(6-tert.butyl-4-ethylphenol),
4,4'-methylene-bis-(6-tert.-butyl-2-methylphenol),
4,4'-methylene-bis-(2,6-di-tert.-butylphenol),
2,6-di-(3-tert.-butyl-5-methyl-2-hydroxybenzyl)-4-(methylphenol,
2,2'-methylene-bis-[4-methyl-6-(alpha-methylcyclohexyl)-phenol],
1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-butane,
2,2-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propane,
1,1,3-tris-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-butane,
2,2-bis-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecyl-mercapto-buta
ne, 1,1,5,5-tetra-(5-tert.-butyl-4-hydroxy-2-methylphenyl)-pentane and
ethylene glycol bis-[3,3-bis-(3-tert.-butyl-4-hydroxyphenyl)-butyrate].
1.5 O-, N- and S-benzyl compounds, such as for example,
3,5,3',5'-tetra-tert.-butyl-4,4'-dihydroxydibenzyl ether, octadecyl
4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate,
tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-amine and
bis-(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.
1.6 Hydroxybenzylated malonates, such as for example, dioctadecyl
2,2-bis-(3,5-di-tert.-butyl-2-hydroxy-benzyl)-malonate, dioctadecyl
2-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)-malonate,
di-dodecylmercapto-ethyl
2,2-bis-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate and
di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]2,2-bis-(3,5-di-tert.-butyl-4-hydr
oxybenzyl)-malonate.
1.7 Hydroxybenzyl-aromatic compounds, such as, for example,
1,3,5-tri-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene,
1,4-di-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene and
2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxy-benzyl)-phenol.
1.8 s-Triazine compounds, such as, for example
2,4-bis-octylmercapto-6-(3,5-di-tert.-butyl-4-hydroxy-anilino)-s-triazine,
2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxy-anilino)-s-triazine,
2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine,
2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxyphenoxy)-s-triazine,
2,4,6-tris-(3,5-di-tert.-butyl-4-hydroxphenylethyl)-s-triazine and
1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl) isocyanurate.
1.9 Amides of .beta.-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acids,
such as, for example
1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-tria
zine and
N,N'-di-(3,5-di-tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamin
e, N,N'-bis-.beta.-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyl-hydrazine.
1.10 Esters of .beta.-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid
with monohydric or polyhydric alcohols, such as for example, with
methanol, ethanol, octadecanol, 1,6-hexanediol; 1,9-nonanediol, ethylene
glycol, 1,2-propane-diol, diethylene glycol, thiodiethylene glycol,
neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thia-pentadecanol,
trimethylhexanediol, trimethyl- olethane, trimethylolpropane,
tris-hydroxyethyl isocyanurate and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.
1.11 Esters of .beta.-(5-tert.-butyl-4-hydroxy-3-methylphenyl)-propionic
acid with monohydric or polyhydric alcohols, such as for example, with
methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, di-ethylene glycol, thiodiethylene glycol,
neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thia-pentadecanol,
trimethylhexanediol, trimethylole- ethane, trimethylolpropane,
tris-hydroxyethyl isocyanurate and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]- octane.
1.12 Esters of 3,5-di-tert.-butyl-4-hydroxyphenylacetic acid with
monohydric or polyhydric alcohols, such as for example, with methanol,
ethanol, octadecanol, 1,6-hexandiol, 1,9-nonanediol, ethylene glycol,
neopentyl glycol, pentaerythritol, 3-thia-undecanol, -thiapentadecanol,
trimethylhexanediol, trimethylolethane, trimethylolpropane,
tris-hydroxyethyl isocyanurate and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-[2.2.2]-octane, especially
the tetrakis ester of pentaerythritol.
1.13 Benzylphosphonates, such as, for example, dimethyl
2,5-di-tert.-butyl-4-hydroxybenzylphosphonate, diethyl
3,5-di-tert.-butyl-4-hydroxybenzylphosphonate, dioctadecyl
3,5-di-tert.-butyl-4-hydroxybenzylphosphonate and dioctadecyl
5-tert.-butyl-4-hydroxy-3-methylbenzylphosphonate.
2. Light-stabilizers
2.1 Esters of optionally substituted benzoic acids, e.g.,
3,5-di-tert.-butyl-4-hydroxybenzoic acid, 2,4-di-tert.-butyl-phenyl ester
or -octadecyl ester or 2-methyl-4,6-di-tert.-butyl-phenyl ester.
2.2 Sterically hindered amines e.g..,
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethyl-piperidine,
bis-(2,2,6,6-tetramethylpiperidyl) sebacate,
bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,
bis-(1,2,2,6,6-pentamethylpiperidyl)
2-n-butyl-2-(2-hydroxy-3,5-di-tert-butyl-benzyl)malonate or
3-n-octyl-7,7,9,9-tetra-methyl-1,3,8-triazaspiro[4.5]decane-2,4-dione.
2.3 Oxalic acid diamides, e.g., 4,4'-di-octyloxy-oxanilide,
2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide,
2,2'-di-dodecycloxy-5,5'-di-tert.-butyl-oxanilide,
2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethyl-aminopropyl)-oxalimide,
2-ethoxy-5-tert.-butyl-2'-ethyl-oxanilide and the mixture thereof with
2-ethoxy-2'-ethyl-5,4'-di-tert.-butyl-oxanilide, or mixture of ortho- and
paramethoxy- as well as of o- and p-ethoxy-di-substituted oxanilides.
3. Metal deactivators, e.g., oxanilide, isophthalic acid dihydrazide,
sebacic acid-bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide,
N,N'-diacetal-adipic acid dihydrazide, N,N'-bis-salicycloyl-oxalic acid
dihydrazide, N,N'-bis-salicyloylhydrazine,
N,N'-bis-(3,5-di-tert.-butyl-4-hydroxy-phenylpropionyl)-hydrazine,
N-salicyloyl-N'-salicylalhydrazine, 3-salicyloyl-amino-1,2,4-triazole or
N,N'-bis-salicyloyl-thiopropionic acid dihydrazide.
4. Basic co-stabilizers, e.g., alkali metal salts and alkaline-earth metal
salts of higher fatty acids, for example Ca-stearate, Zn-stearate,
Mg-behenate, Na-ricinoleate or K-palmitate.
5. Nucleation agents, e.g., 4-tert.-butylbenzoic acid, adipic acid or
diphenylacetic acid.
6. Phosphites and phosphonites, such as, for example, triphenyl phosphite,
diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonyl-phenyl)
phosphite, trilauryl phosphite, trioctadecyl phosphite and
3,9-iso-decyloxy-2,4,8,10-tetraoxa-3,9-diphospha-[5.5]-undecane and
tetra(2,4-di-tert-butylphenyl) diphenylene-4,4'-bis(phosphonite).
Other additives that can be incorporated in the stabilized compositions are
thiosynergists such as dilauryl thiodipropionate, lubricants such as
stearyl alcohol, fillers, asbestos, kaolin, talc, glass fibers, pigments,
optical brighteners, flameproofing agents and antistatic agents.
The following examples are presented for the purpose of illustration only
and are not to be construed to limit the nature or scope of the instant
invention in any manner whatsoever.
EXAMPLES 1-11
In a flask fitted with a nitrogen blanket, stirrer, reflux condenser and
addition funnel, 0.5 mole of olefin, 0.5 mole of the 2H-benzotriazole and
0.5 mole of 98% methanesulfonic acid are heated to 160.degree. C. and held
at this temperature for a period of four hours during which time an
additional 1.5 moles of olefin are added to the reaction mixture.
The mixture is then cooled to 20.degree. C. The lower methanesulfonic acid
layer is separated off and the upper olefin-product layer is washed once
with 1000 ml of 2% sodium carbonate solution and finally dried over
anhydrous magnesium sulfate.
The dried organic solution is vacuum stripped at 170.degree. C./0.5 mm Hg
to remove the unreacted olefin. The residual material is then vacuum
distilled on a Kugelrohr column to give a fraction boiling at about
170.degree.-180.degree. C./0.1 mm Hg which includes some hydrocarbon
material and the desired at about 180.degree.-210.degree. C./0.05 mm Hg.
The desired products boiling products are in every case viscous yellow
liquids.
The products prepared by the method described above are analyzed by
chemical ionization mass spectrometry using a direct probe inlet. Control
samples of the various starting materials confirm that the observed
product distributions are real and are not artifacts due to fragmentation
inside the mass spectrometer.
______________________________________
Starting 2H-benzotriazole
Example
R.sub.2 G.sub.2 G.sub.3 Olefin
______________________________________
1 tert-butyl -- -- n-dodecene
2 tert-amyl -- -- n-dodecene
3 tert-octyl -- -- n-dodecene
4* tert-octyl -- -- n-dodecene
5 alpha,alpha- -- -- n-dodecene
dimethylbenzyl
(= cumyl)
6 -- tert-butyl
tert-butyl
n-dodecene
7 -- tert-amyl
tert-amyl
n-dodecene
8 -- tert-octyl
tert-octyl
n-dodecene
9 -- cumyl cumyl n-dodecene
10 tert-octyl -- -- propylene
tetramer
11 ethyl -- -- n-dodecene
______________________________________
*Reaction is run with 1 mole of olefin, 1 mole of 2Hbenzotriazole and 0.5
mole of methanesulfonic acid.
The mass spectrometer analyses of the reaction products obtained from
Examples 1-11 are given on Tables 1-11 below.
Tables 1-5 and 10-11 give the results of reacting an olefin with a
2-(2-hydroxy-5-alkyl(or cumyl)phenyl)-2H-benzotriazole. Tables 6-9 show
the results of reacting an olefin with a 2-(2-hydroxy-3,5-di-tert-alkyl(or
cumylphenyl)-2H-benzotriazole.
In Tables 1-5 and 10-11, the "normal" products which would be obtained by
olefin addition to the 2H-benzotriazole without any displacement,
fragmentation or other reaction are asterisked. Such products usually
amount to much less than 50% of the product mixture.
In Tables 6-9, The products obtained by an alkyl exchange reaction where
one alkyl (or cumyl) is replaced by a dodecyl moiety are asterisked. Such
products occur in the 10-36% range of the final product mixture.
TABLE 1
______________________________________
ALKYLATION OF 2-(2-HYDROXY-5-tert-
BUTYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion
Proportion in
in bp 170.degree./
by 180-210.degree./
Mole- Total Carbon
0.1 mm Hg 0.05 mm Hg
cular Atoms in Alkyl
Fraction**
Fraction
Weight
Substituent(s)
(in %) (in %) Comments
______________________________________
267 C.sub.4 6 1
323 C.sub.8 3 1
337 C.sub.9 4
379 C.sub.12 32 40 C.sub.12 only
435 C.sub.16 40* 50* C.sub.4 + C.sub.12
491 C.sub.20 5 4
547 C.sub.24 2 1 2 .times. C.sub.12
or C.sub.24
______________________________________
**This fraction includes hydrocarbons.
TABLE 2
______________________________________
ALKYLATION OF 2-(2-HYDROXY-5-tert-
AMYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion in
Total Carbon bp 180-210.degree./
Molecular
Atoms in Alkyl
0.06 mm Hg
Weight Substituent(s)
Fraction (in %)
Comments
______________________________________
281 C.sub.5 6
337 C.sub.9 2
351 C.sub.10 2
379 C.sub.12 36 C.sub.12 only
421 C.sub.15 3
435 C.sub.16 4
449 C.sub.17 38* C.sub.12 + C.sub.5
491 C.sub.20 2
505 C.sub.21 2
______________________________________
TABLE 3
______________________________________
ALKYLATION OF 2-(2-HYDROXY-5-tert-
OCTYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion
Proportion in
in bp 170.degree./
by 180.degree./
Mole- Total Carbon
0.1 mm Hg 0.03 mm Hg
cular Atoms in Alkyl
Fraction Fraction
Weight
Substituent(s)
(in %) (in %) Comments
______________________________________
267 C.sub.4 8
281 C.sub.5 3
323 C.sub.8 11 4 starting
material or
isomers
337 C.sub.9 5 2
351 C.sub.10 3 2
365 C.sub.11 4 4
379 C.sub.12 30 37 C.sub.12 only
393 C.sub.13 3 3
421 C.sub.15 5
435 C.sub.16 9 13 C.sub.4 + C.sub.12
491 C.sub.20 18* 23* C.sub.8 + C.sub.12
547 C.sub.24 3 3 2 .times. C.sub.12
______________________________________
TABLE 4
__________________________________________________________________________
ALKYLATION OF 2-(2-HYDROXY-5-tert-OCTYLPHENYL)-
2H-BENZOTRIAZOLE WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion in
Total Carbon
bp 140-70.degree.
Proportion in in
Proportion overall
Molecular
Atoms in Alkyl
Fraction 2-10
Fraction bp 170-180.degree. C.
Proportion overall
Weight
Substituents
mm Hg (in %)
0.05 mm Hg (in %)
calcd. (in %)
Comments
__________________________________________________________________________
211 0 10.6 -- 8.1 Fully de-
alkylated
product
267 C.sub.4 23.5 0.5 18.1
323 C.sub.8 41 24.6 37.2 Starting
material
and/or
isomers
365 C.sub.11
3.7 3.1 3.5
379 C.sub.12
14.7 27.4 17.6 Loss of C.sub.8
and Addition
of C.sub.12
421 C.sub.15
1.0 2.5
435 C.sub.16
2.0 8.7 3.5
491 C.sub.20
1.5* 20.6* 5.9* C.sub.8 + C.sub.12
"normal
product"
547 C24 0.1 2.3 0.6 2 .times. C12
__________________________________________________________________________
TABLE 5
______________________________________
ALKYLATION OF 2-(2-HYDROXY-5-
CUMYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion in bp
Total Carbon by 180-210.degree./
Molecular
Atoms in Alkyl
.04 mm Hg
Weight Substituent(s)
Fraction (in %)
Comments
______________________________________
379 C.sub.12 73 C.sub.12 only
421 C.sub.15 6
435 C.sub.16 4
497 C.sub.21 12* C.sub.12 + Cumyl
547 C.sub.24 5
______________________________________
TABLE 6
______________________________________
ALKYLATION OF 2-(2-HYDROXY-3,5-DI-tert-
BUTYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion
Proportion in
in bp 160.degree./
by 190-202.degree./
Mole- Total Carbon
1.0 mm Hg .01 mm Hg
cular Atoms in Alkyl
Fraction Fraction
Weight
Substituent(s)
(in %) (in %) Comments
______________________________________
211 0 2 --
267 C.sub.4 5 1
323 C.sub.8 5 2
337 C.sub.9 4 1
351 C.sub.10 2 1
365 C.sub.11 3 3
379 C.sub.12 35 44 C.sub.12 only
393 C.sub.13 3 2
435 C.sub.16 28* 36* C.sub.4 + C.sub.12
491 C.sub.20 6 7
547 C.sub.24 3 2
______________________________________
TABLE 7
______________________________________
ALKYLATION OF 2-(2-HYDROXY-3,5-DI-tert-
AMYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion in
Molecular
Total Carbon Atoms
by 180-205.degree./.05 mm Hg
Weight in Alkyl Substituent(s)
Fraction (in %)
______________________________________
337 C.sub.9 1
351 C.sub.10 2
379 C.sub.12 42
393 C.sub.13 3
435 C.sub.16 11
449 C.sub.17 35*
491 C.sub.20 3
547 C.sub.24 2.5
______________________________________
TABLE 8
______________________________________
ALKYLATION OF 2-(2-HYDROXY-3,5-DI-tert-
OCTYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion in
Total Carbon
bp 185-202.degree./
Molecular
Atoms in Alkyl
.06 mm Hg
Weight Substituent(s)
Fraction (in %)
Comments
______________________________________
267 C.sub.4 2
281 C.sub.5 1
309 C.sub.7 2
323 C.sub.8 12 C.sub.12 only
337 C.sub.9 2
351 C.sub.10 1
365 C.sub.11 3 C.sub.12 + C.sub.5
379 C.sub.12 17
435 C.sub.16 46 C.sub.12 + C.sub.4 and/
or C.sub.8 + C.sub.8
491 C.sub.20 10*
547 C.sub.24 1
______________________________________
TABLE 9
______________________________________
ALKYLATION OF 2-(2-HYDROXY-3,5-
DICUMYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion in
Total Carbon
bp 180-210.degree./
Molecular
Atoms in Alkyl
0.05 mm Hg
Weight Substituent(s)
Fraction (in %)
Comments
______________________________________
211 0 1 Fully de-
alkylated
product
323 C.sub.8 1
365 C.sub.11 1
379 C.sub.12 72 C.sub.12 only
435 C.sub.16 3
497 C.sub.21 20* C.sub.12 + cumyl
______________________________________
TABLE 10
______________________________________
ALKYLATION OF 2-(2-HYDROXY-5-tert-
OCTYLPHENYL)-2H-BENZOTRIAZOLE
WITH PROPYLENE TETRAMER
COMPOSITION ANALYSIS
Proportion in
Total Carbon
bp 200-210.degree./
Molecular
Atoms in Alkyl
0.05 mm Hg
Weight Substituent(s)
Fraction (in %)
Comments
______________________________________
365 C.sub.11 4
379 C.sub.12 14 C.sub.12 only
393 C.sub.13 5.5
407 C.sub.14 5
421 C.sub.15 7.5
435 C.sub.16 13 C.sub.12 + C.sub.4
449 C.sub.17 8
463 C.sub.18 7
477 C.sub.19 8
491 C.sub.20 13* C.sub.12 + C.sub.8
505 C.sub.21 5.5
519 C.sub.22 3.5
547 C.sub.24 4.5
______________________________________
TABLE 11
______________________________________
ALKYLATION OF 2-(2-HYDROXY-5-
ETHYLPHENYL)-2H-BENZOTRIAZOLE
WITH n-DODECENE
COMPOSITION ANALYSIS
Proportion in
Total Carbon
bp 180-210.degree./
Molecular
Atoms in Alkyl
0.06 mm Hg
Weight Substituent(s)
Fraction (in %)
Comments
______________________________________
239 C.sub.2 8.0
267 C.sub.4 1.5
281 C.sub.5 1.5
295 C.sub.6 2.6
309 C.sub.7 1.9
323 C.sub.8 1.6
351 C.sub.10 2.1
379 C.sub.12 6.2 C.sub.12 only
407 C.sub.14 62.7* C.sub.12 + C.sub.2
433 C.sub.16 4.0
449 C.sub.17 4.1
463 C.sub.18 3.8
547 C.sub.24 0.2
575 C.sub.26 0.9
______________________________________
EXAMPLE 12
To a 1-liter reaction flask fitted with a nitrogen blanket, stirrer, dosing
device with proportion pump and distillation column connected with a
condensation trap and water jet vacuum pump is charged 323 grams (1 mol)
of 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole and 96.1 grams
(1 mol) of methanesulfonic acid. The reaction flask is swept with
nitrogen. Then, without stirring, the mixture is melted by heating to
about 150.degree. C. Heating is now continued with stirring to a
temperature of 175.degree. C. At this temperature, 234 grams (1.02 mol) of
n-hexadecene are added below the surface of the mixture through the dosing
device over a 6-hour period. The reaction mixture is then heated for
another 30 minutes at 175.degree. C. The mixture is then cooled to about
95.degree. C. and extracted with 100 ml of water, 100 ml of 4% sodium
bicarbonate solution and again with 100 ml of water. Then, 100 grams of
bleaching earth (Prolith Rapid) are added and the water is distilled off
at 100.degree. C./20 mbar. The bleaching earth is removed by filtration to
give 532 grams (corresponding to a yield of 95% of theory) of a yellow to
brownish-yellow liquid. This liquid is further purified by distillation in
a thin-film evapoarator at 285.degree. C./1-3 mbar. The yellow liquid
product has an n.sub.D 20 of 1.5362.
EXAMPLES 13-17
Using the general procedure of Example 12, alkylation of
2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole with other
1-alkenes affords the following liquid products.
______________________________________
Yield n.sub.D.sup.20
Example
1-Alkene % of theory)
(of product)
______________________________________
13 n-octene 84 --
14 n-decene 90 1.5778
15 n-dodecene 82.9 1.5662
16 n-tetradecene
95 1.5550
17 n-octadecene 94 1.5229
______________________________________
EXAMPLE 18
Following the general procedure of Example 12, 286.3 grams of (0.8 mol) of
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole are
reacted with 165 grams (0.84 mol) of n-tetradecene in the presence of 96.1
grams (1 mol) of methanesulfonic acid to give a liquid product in a yield
of 86% of theory.
EXAMPLE 19
Following the procedure of Example 12,
5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole is reacted
with n-octadecene to give a liquid product with an n.sub.D 20 of 1.5378.
EXAMPLE 20
Following the general procedure of Example 12, 323 grams (1 mol) of
2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole are alkylated with 171.5
grams (1.02 mol) of n-dodecene in the presence of 96.1 grams (1 mol) of
methanesulfonic acid to give a liquid product in a 92% yield of theory
with an n.sub.D 20 of 1.5678.
EXAMPLES 21-25
In like manner as is Example 20,
2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole is alkylated with other
1-alkenes to give the following products.
______________________________________
Yield n.sub.D.sup.20
Example
1-Alkene (of theory)
(of product)
______________________________________
21 n-octene 88 1.5757
22 n-decene 100 1.5663
23 n-tetradecene
90 1.5465
24 n-hexadecene 91 1.5436
25 n-octadecene 91.3 1.5360
______________________________________
EXAMPLE 26
Following the general procedure of Example 12, 351 grams (1 mol) of
2-(2-hydroxy-3,5-di-tert-amylphenyl)-H-benzotriazole are reacted with
200.3 grams (1.02 mol) of n-tetradecene in the presence of 96.1 grams (1
mol) of methanesulfonic acid to give a liquid product in a yield of 88% of
theory with an of 1.5293.
EXAMPLES 27-30
In the same manner as in Example 26,
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole is alkylated with
other 1-alkenes to give the following liquid products.
______________________________________
Yield n.sub.D.sup.20
Example
1-Alkene (% of theory)
(of product)
______________________________________
27 n-octene 86 --
28 n-decene 87.5 1.5913
29 n-dodecene 82 1.5418
30 n-octadecene 87 1.5158
______________________________________
EXAMPLE 31
Following the procedure of Example 12, 315.8 grams (1 mol) of
5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole are
alkylated with 176.5 grams (1.05 mol) of n-dodecene in the presence of
96.1 grams (1 mol) of methanesulfonic acid to give a liquid product in a
yield of 57% of theory with an n.sub.D 20 of 1.5852.
EXAMPLE 32
A thermoset acrylic resin coating composition, typical for automotive
topcoats, is formulated with 2% by weight of the light stabilizer prepared
in Example 2. The coating composition is applied to a metal panel and
baked at 130.degree. C. to cure the resin. The coated panel is then
exposed to accelerated (quick) weathering test (QUV) involving alternating
8-hour period of UV irradiation at 70.degree. C. with a 4-hour period of
condensation (rain) at 50.degree. C. for each cycle.
The 20.degree. gloss (ASTM D523 and D2457) and the Distinctness of Image
(ASTM E 430) values for the coating before and after weathering in the QUV
test are measured and the % retention of 20.degree. gloss and of
distinctness of image (D/I) are calculated. The control is the same
thermoset acrylic resin coating containing no stabilizer.
The coating containing the instant stabilizer of Example 2 has far better
gloss retention, a much higher % retention of D/I and a surface that did
not crack compared to the control coating.
The stabilized coating exhibits far superior gloss and D/I retention than
the unstabilized control. The stabilized sample shows no sign of surface
cracking or crazing again showing the efficacy of the instant compounds as
light stabilizers.
EXAMPLE 33
An oil-modified urethane varnish containing 2% by weight of the stabilizer
prepared in Example 7 is coated on an aluminum panel and exposed outdoors
at a 90.degree. angle facing south in Southern New York for a period of
10.5 months.
The yellowness index (YI), measured by ASTM D 1925, for the sample is
measured before exposure and after exposure. The change in YI is a measure
of how much the urethane coating discolored over the test period. The
lower the change in YI the less discolored is the sample.
The urethane varnish containing the instant benzotriazoles of Example 7
does not yellow whereas the control (without stabilizer) turns
perceptively discolored (yellowed).
EXAMPLE 34
Haze Development in Photographic Compositions
The direct assessment of the compatibility of benzotriazole light
stabilizers in photographic composition is difficult. The compositions
containing such stabilizers in photographic oils often take extended
periods of time for separation or haze to be observed.
An important property of photographic compositions directly related to such
compatibility parameters is haze. For the preparation of clear and precise
photographic images, haze must obviously be minimized or better yet
essentially eliminated.
Using the procedure described in U.S. Pat. No. 4,383,863, Example 5, a
UV-protecting layer is prepared in gelatin containing an anionic wetting
agent, a hardener and the instant stabilizer of Example 10 using no
solvent.
A very fine dispersion of the instant stabilizer in this gelatin
composition is produced by ultrasonic mixing to give a UV-protecting layer
which is clear and transparent and exhibits no haze.
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